Bonding butyl rubber to nylon



United States Patent 3,111,448 BONDING BUTYL RUBBER TO NYLON Pliny 0.Tawney, Passaic, N .J assignor to United States Rubber Company, NewYork, N.Y., a corporation 0? New Jersey N0 Drawing. Filed Feb. 3, 1959,Ser. No. 790,810

16 Claims. (Cl. 16192) This invention relates to new high temperatureadhesives for bonding butyl rubber to nylon textile materials, themethods of efiectuating such bonding, and the products so formed.

Heretofore it has been extremely diliicult to bond butyl rubber tonylon, and the bonds have been weak at the high temperatures, e.g.,2503GO F., reached inside an automobile tire in operation.

Many adhesives which contain reso-rcinol or its reaction products withformaldehyde are known. See, e.g., Charch and Maney U.S. Patents2,128,229 and 2,128,635; Jordan US. Patent 2,188,736. They are used tobond various textile materials to rubbers. However, in general they arenot suitable for bonding butyl rubber to textile materials such asnylon, because the bond is not strong enough at high temperatures to beuseful in tires. Perhaps the best is Essos experimental butyl latexmixed with resorcinol and formaldehyde, but it is hardly good enough fortires, it is described by A. L. Miller et al., Rubber World 137, 3974(3, 460 (1957). The adhesion data given therein are for adhesive bondstrengths at room temperature only; i.e., no data are given for adhesionat high temperatures, e.g., 250 F., attained inside a tire.

Thus, it has been impossible to build a serviceable tire in which butylrubber was bonded directly to nylon tire cord. Such a tire, especiallyan ail-butyl tire, would be extremely valuable because of theextraordinary resistance of butyl to attack by oxygen, the quietness ofb'utyl treads on the road, and the fact that no inner tube nor specialinner lining is needed to retain air in the tire. This invention solvesthe problem of bonding butyl rubber directly to nylon textile materialsand allows one to make tires and other products in which the bondbetween butyl. rubber and nylon cord retains very high strength whfenhot.

The invention consists of a cement or dispersion co=mprising (1) acompound selected from the class consisting of the dihydric phenols ofthe benzene and naphthalene series; and (2) a phenolic dialiranolmaterial se-- lected from the class consisting of (a) compounds havingthe structure (i) XO- cin o tnox I Y n where R and X independently arechosen from hydrogen and lower acyl, and where Y is chosen from alkyl,cyclo alkyl, aryl, aralkyl, chloro, and nitro, and n is an integer inthe range from one to three inclusive; (1)) selfcondensation polymers ofthose compounds of Formula I 3,111,448 Patented Nov. 19, 1963 in which Rand X are hydro-gen and wherein Y is chosen from alkyl, cycloalkyl, aryland arallyl, and n is one; and (0) compounds having the structure IIO'lovrcr alkyl IIOCIIz CH2OII where Y is the same as in structure I. Inanother aspect the invention consists of the method of bonding butylrubber to nylon by this cement or dispersion, and the composite articlesthus formed, wherein the butyl contains a curing agent selected from theclass consisting of the self-condensation polymers defined in b above,and the monomers corresponding to said polymers. More particularly, themethod of the invention comprises building up alternating layers ofnylon textile material and butyl rubber coated with my novel adhesive,and heating the composite material to vulcanize the butyl rubber andform a unitary, cohesive article.

The term lower refers to alkyl groups containing not more than fourcarbon atoms. When the material I contains more than one group Y thegroups can be alike or clilferent.

Optionally, the materials I and II also may have methyl groups in the 3-and 5-positions, numbering from the OR or O-lower alkyl group in thel-position.

By definition, in this invention the selfcondensation polymers are thematerials which are formed from the defined compounds by heating them,in the presence or absence of an alkaline or acidic catalyst, to such atemperature that water and/or formaldehyde is evolved.

The term butyl rubber as used herein refers to that known class ofsynthetic rubbers typically made by low temperature copolymerization ofan isoolefin with a minor amount of a multi-olcfinic unsaturate. Theisoolctins used generally have from 4 to 7 carbon atoms, and suchmonoisooletins as isobutylene and 2-methyl-2- butene are preferred.

The multi-olefinic unsaturate is generally a conjugated diolefin usuallyhaving from 4 to 8 carbon atoms. The most important of these diolelinsare isoprene and butadiene; others are piperylene,2,3-dimethylbutadiene, 3- methyl-l,3-pentadiene,2-inethyl-1,3-pentadiene, 1,3-hexadienc and 2,4-hcxadiene. The basiccopolymer may be modified, if desired, either by including othercopolymerizable matenials such as chloroprene, allyl chloride ormethallyl chloride in the original preparation of the copolymer, or bytreating the previously prepared copolyrner with reactive reagents suchas maleic anhydride, bromine or chlorine. Thus, the content of isoolefinmay vary from to 99.5%, depending on whether additional monomers arepresent. If there is no additional modifying co-monomer present, theisoolefin content usually amounts to from to 99.5%. Hence, theexpressions butyl rubber, or rubbery copolymer of an isoolefin with from0.5 to 10% of a diolefin, or similar expressions, as used hereintherefore contemplates the various known modified forms of a butylrubber copolymer, as well as the unmodified copolymer.

Typical methods of compounding and curing the butyl rubber are given byTawney et al. in U.S. Patent 2,701,- 895 issued on February 15, 1955,and in copending application of Viohl, Serial No. 644,980, filed March11, 1957, now Patent No. 2,918,448.

The dihydric phenols of the benzene and naphthalene series which 1 usein my adhesives include benzenediols, e.g., catechol and the preferredresorcinol and hydroquinone; and naphthalenediols, e.g.,1,2-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenedioi, etc.These phenols include those which have alkyl groups in addition to thetwo free hydroxyl groups. Typical substituted phenols arep-tert-butylcateehol, toluhydroquinone, 2,5- di-tert-butylhydroquinone,orcinol, 2-rnethyl-1,4-naphthaienediol, and Ln-hexylresorcinol.

Typical compounds which have the structure I are the preferred2,6-dimethylol-4-tert-butylphenol, and

2.6-dimethylol-4-methylphcnol; 2,6-dimethylol-4-cyclohexylphenol;2.6-dimethy]ol-4-benzylphenol;2,6-dimethylol-4-alpha,alpha-dimethylbenzylphenol;2.2'-methylene-bis-(4-tert-butyl-fi-methylolphenol2.2-methylene-bis-(4-chloro-6-methylolphenol 2 6-bis- 2'hydroxy-3-methylo1-5 -tert-butylbenzyl -4-tertbutylpheno];2,6-bis-(acetoxymethyl)-4-tertbutylphenol;2,6-bis-(acetoxyrnethyl)-4-tert-butylphenyl acetate;2,2-methylene-bis-(4-nitro-6-aeetoxymethylphenol);2,6-bis-(2-hydroxy'3-acetoxymethyl-S-tert-butylbenzyl)-4tert-butylphenol;2,6-bis(2-acetoxy-3-acetoxymethyl-S-tert-butylbenzyl)-4-tert-butylphenyl acetate; and2,6-bis-(propionoxymethyl)-4-tert-tertoctylphenol.

The hydrocarbon radicals comprising the Y substituents of structuralFormulas I and II may in turn bear substituents, viz., such groups asnitro. halogen, carboxyl, cyano, earboxyester and carboxamide. Themaximum acceptable number of carbon atoms in the Y substituent istwelve, as exemplified by the dodecyl [CH (CH group.

The methylol compounds of structural class I can be made as shown byTawney et a]. in US. Patent 2,701,895 issued February 15, 1955, and incopending application of Viohl, Serial No. 644,980, filed March 11,1957. The acylates whose phenolic groups are free can be made as shownin U.S. Patent 2,830,970 (issued April 15, 1958 to Tawney). The aeylateswhose phenolic groups and whose methylol groups are esterified can bemade as shown in US. Patent 2,825,720 (issued March 4, 1958, to Tawney).

Typical, commercially available self-condensation polymers are SuperBeckacites 1001 and 1003, which are said to be formed byalkaline-catalyzed reaction between 4- tert-butylphenol andformaldehyde, and Amberol ST- 137, which is said to be formed by thealkaline-catalyzed reaction between 4-tert-tert-oetylphenol andformaldehyde. Self-condensation polymers can also be made by heating thecorresponding monomeric 2,6-dimethylolphenols, either alone or in thepresence of a small amount of acid or alkali, as shown in US. Patent2,701,895, Example 7.

Typical compounds which have the structure II are ethyl2,6-dirnethylol-4-methylphenyl ether and methyl2,6-dimethylol-4-tert-butylphenyl ether. They can be made as shown byvan der Meer, Rubber Chem. Tech.

The adhesive composition can be used either as an aqueous dispersion oras a solution in a solvent medium. An aqueous dispersion can best beused when the methylolated material is a condensation polymer, althoughthe polymers also can be used in solution. The monomericdimethylolphenols are most often used in solution.

Dispersions are easily made by grinding the solid condensation polymerwith water and a small amount (0.025 to 1.0% by weight based on thepolymer) of dispersing agent such as methyicellulose in, say, a paintmill or by some other conventional means. The dihydric phenol can bedispersed or dissolved in the medium in the step of dispersing thecondensation polymer. Alternatively, if the dihydric phenol is quitesoluble in water, e.g., catechol, resorcinol or hydroquinone, it can beadded to the previously formed dispersion.

When the adhesives are used in the form of a solvent cement the choiceof a solvent medium will depend on the solubility characteristics of theparticular solute mixture of dihydric phenol and dimethylol materialused. No rigid specifications can be made because this solute mixturecan be varied exceedingly widely. Particular media suitable for anyparticular solute mixture can be found easily by experiment. The workingexamples show how to carry out such experiments, and show typicalsolven-solute formulations. Other solvents operable in this inventioninclude the kctones (e.g., methyl ethyl ketone), esters (e.g., ethylacetate), aliphatic ethers (e.g., diethyl ether), and the cyclic otherssuch as dioxane and tetrahydrofuran.

In practical embodiments of the invention nylon tire cord is passedthrough the solution or dispersion of the adhesive mixture, dried atroom temperature or in a hotair oven, and built conventionally into abutyl carcass of a tire. The tire is then assembled and curedconventionally. The euring agent in the carcass must be one of thephenol dialcohols which cures at a practical rate, such as the curingagents disclosed in US. Patent 2,701,895. These curing agents may bedescribed as condensation polymers of 2,6'dimcthylol-4hydroearbonphenols(i.e., multieyclic) and the monomers corresponding to said polymers(i.e., monocyclic).

Examples of monocyclic phenol dialcohols include 2,6- dirnethylol4-tert-butylphenol; 2,6-dirnethylol-4-phenylphenol;2,6-dimethylol4-benzylphenol; 2,6-dimethylol-4-alpha,alpha-dimethylbenzylphenol and many others wherein the parasubstituent is hydrocarbon radical.

Multicyelic phenol dialcohols are condensation polymers which can beformed as shown in the Carswell volume entitled Phenoplasts published byInterscience Publishers, New York, 1950, on pp. 1722 by heating thecorresponding monocyelic dialcohol.

The rate at which the cord is passed through the adhesive can be variedwidely without adversely affecting the adhesion. However, at a highspeed the cord picks up more adhesive than at a lower one. As the amountof dried adhesive on the cord should be held within certain limits it isnecessary to use a somewhat more dilute solution or dispersion of theadhesive when running at high speed than when running at lower speed.

Exact limits for the invention cannot be given because of the greatnumber of combinations of dihydric phenols and methylolated materials,and because of the various conditions under which the adhesives are tobe used. Therefore, one important embodiment of the invention will nowbe described, limits concerning this embodiment will be set, andindications as to how to apply these findings to other embodiments ofthe invention will be given.

This embodiment has to do with the use of adhesive mixtures ofresorcinol and 2,6-dimethylol-4-tert-butylphenol, in proportions rangingfrom about 20:80 to about :20 (by weight).

The solid content of the adhesive solution can range between about 5%and about 15% by weight. The amount of adhesive picked up by cordtravelling through a bath of such an adhesive solution at a speed of2-16 yards per minute will be within the acceptable limit of from about0.75% to about 5% of dried adhesive based on the weight of the cord. Ifthe pickup is less than about 0.75% or materially more than about 5%,adhesion will be poor.

The adhesive solution may he used immediately after preparation or itmay be kept for weeks at room temperature Without deterioration.

The dipped cords may be dried at room temperature or at elevatedtemperature under conditions at least as drastic as an hour at 250 F.without harm. Indeed, the coated cords have been dried as high as 300 F.without causing any adverse effect on the final adhesion. At atemperature of 250 F. not only does the adhesive become dried, but alsothe solid materials react to form an alcohol-insoluble resin on thecord. The time required to drive off the carrier liquid for the adhesivecomponents varies inversely with the temperature, and is determined byexperiment. Generally, 3 minutes at 300 F. is sutficient for an 80:20mixture of 95% ethanol and water Whereas at 250 F. a reasonable dryingtime for this same mixture would be 15 minutes.

The following examples illustrate the invention. Adhesive strengths weredetermined by the so-called H-test" described by Lyons, Nelson andConrad-India Rubber World, 114, 213 et seq. (1946)-at 250 F. and in manycases at room temperature. In all pairs the adhesion at room temperaturewas much higher than that at 250 F. Comparison between the H-test androad tests of tires showed that if the I-I-adhesion at 250 F. was atleast about 10 pounds the adhesion of the cord to the rubber in the tirewould be adequate both at ambient air temperature and at the hightemperatures normally found in a tire carcass during operation.Therefore, for brevity in the following examples only the H-adhesion at250 F. Will be shown. All parts and percentages are by weight.

Example 1 An 840/2-ply nylon tire cord of conventional construction waspassed under slight tension through the different adhesive solutionsdescribed below at a rate of six feet per minute, and was then dried,while still under tension, for three minutes in air at 300 F. Then thecoated cord was embedded, in an H-tcst mold, in a conventional, uncuredbutyl stock containing a phenol dialcohol curing agent, and the assemblywas heated in a mold for 60 minutes at 166 C. The H-adhesion at 250 F.then was determined.

The butyl stock was made as follows:

A masterhatch was mixed in a Banbury internal mixer in the proportion of10-0 parts of HR (formerly called GR-I, a commercial butyl rubber madefrom isobutylone and isoprene), 40 parts of carbon black, and 1.4 partsof Super Beckacite 1001. The mixture then was masticatcd for 10 minutesin the Banhury at 350 F. in order to lower the hysteresis of theultimate cured stool-1s. It then was mixed on a rubber mill with 5 partsof zinc stearate, 2.5 parts of paratl'i nic oil, and 8.6 parts of SuperBeckacite 1001.

The adhesive solutions, including all the controls except those forspecimens 1 and 2, contained solids by weight. The solvent in all casesWas an 80:20 mixture of 95% ethanol and water.

H-adhesion (lbs) Sptclmtn Adhesive Solvent. Al ne Esso butyllatcxItesoruinol l3 2,6-1)luirthylol-4-tert-hutylphenol: Resorclcinol(50:50).

6 2,6-Diinethylol-l-tcrt-butylphenol: ReSOrcl- 7 1-Z-U-Dimet1iyloli-tcrt-butylphenol: Rcsorninol, (:80).

6 4-tert-butylphenol alone. Only specimens 5-7 illustrate thisinvention. Specimens 1-4 are controls.

Example 2 These specimens were made and tested as was specimen 5 ofExample 1 except that the composition of the solvent was varied asshown.

Specimen Solvent II-a dheslon (lbs) 5 95% ethanol: 11:0(811120) 1- 15. 3

Isopropnnol: 1120 (:20). 14.5

. 1, Isopropanol: 11 0 (50:50) 13. 9

This example shows that the solvent medium of the adhesive solution canbe modified extensively without greatly affecting adhesion.

Example 3 These specimens were made and tested as was specimen 5 ofExample 1 except that the dihydric phenol was varied.

Specimen D ihydrlc Phenol Tlhdheslon tlbs.)

llydr'm uinonc n 13.!

This example illustrates the use of several typical dihydric phenolswhich can be used as one of the components of the adhesive mixture.

Example 4 These specimens were made and tested as was specimen 5 ofExample 1 except that various phenoldialcohols Were used.

The above example demonstrates the practice of this invention withformulations of adhesives made from a variety of mononuclear,binuclettr, and trinuclear phenol dialcohols.

Example 5 These nylon-butyl specimens Were made and tested as wasspecimen 5 of Example 1 except that the total solids content of theadhesive solutions was varied. To determine the amount of adhesivepicked up, part of each dried cord was exhaustively extracted with warmethanol (10 minutes), and the amount of rcsorcinol and2,6-.llmethylol-4-tert-butylphenol in the extract was measured by ultraviolet absorption (this method is more accurate than a directdetermination of the increase in weight of the cord when the combinationof drying time and drying temperature is too mild to cause formation ofalcohol-insoluble resorcinol 2,6-dimethylol-4-tert-butylphenol resin;the ultra violet absorption method is unsuitable when the cord is driedfor, say, an hour at 300 F. because of this resin formation). Anotherpart of the dried cord was made into H-test pieces and tested.

Specimen 23 2t 25 2U 27 Total solids (percent) 1O 3t) Adhesive pickup(percent of cord Weight) 0. 80 3.01 4. 66 f. 24 8. 5 II-adln-sion (lbs)12.1 14.3 13.1 I. 7 3. 5

This example shows that the amount of dried adhesive on the cord iscritical and should not exceed a maximum of about 5% based on the weightof the cord. Only specimens 23-25 illustrate this invention.

Example 6 These nylon-butyl specimens were made and tested as wasspecimen 5 of Example 1, except as shown individually. In eachexperiment equal weights of Amberol ST-137 and resorcinol were dissolvedor dispersed in the B Dispersions were made ina paint. mill, usingl\1eth0cel"as dispersing agent.

b Dipped cord was dried for 60 minutes at 250 F. This exampledemonstrates the practice of this invention using a typical adhesiveformulation which can be applied either as an aqueous dispersion or as asolution in a mixture of ethanol and xylene.

Example 7 These specimens were made and tested as was specimen 5 ofExample 1 except that various esters of phenol dialcohols were used.

This example shows that derivatives of phenol dialcohols, wherein themethylol groups and/ or the phenol groups are esterified, can be used inthe practice of this invention.

Example 8 These specimens were made and tested as was specimen 5 ofExample 1 except that (a) methyl 2,6-dimethylol- 4-tert-butyl-phenylether was used instead of the corresponding free phenol, (b) theproportion of resorcinol: ether was varied as shown, (6) the total solidcontent of the adhesive solution was varied as shown, and (d) thesolvent was p-dioxan.

Specimen Ingredients in Adhesive Solution Methyl 2,ddimethyloll-tert-butylphenyl ether 2. 5 1. (I 8. 0 5. U 2.0 Resoreinolu2. 5 4.0 2. U 5.0 8, 0 Dioxun 95.0 95. 0 90. 0 00. U 90. 0 lI-adheslon(lbs.) 13. 4 15. (J 12. 0 15.1 10. 9

This example shows that a derivative of a phenol dialco- 1101, whereinthe phenol group is etherified, can be used in the practice of thisinvention.

Having thus described my invention, what I claim and desire to protectby Letters Patent is:

1. A method of bonding nylon. textile material to rubber, said rubberbeing a copolymer of an isooiefin with a minor amount of a multiolefinicunsaturate, comprising (A) passing said nylon textile material into andthrough a bath of adhesive composition comprising: (i) a compoundselected from the group consisting of dihydric Phenols of the benzeneand naphthalene series, intimately mixed with (2) a phenolic dialkanolcompound selected from. the group consisting of (0) compounds having thestructural Formula I X0 GII: CIIzOX i Y n where R and X independentlyare selected from the group consisting of hydrogen atoms and acylradicals having less than 4 carbon atoms, and where Y is selected fromthe group consisting of chlorine atoms, and alkyl, cycloalkyl, aryl,aralkyl, and nitro radicals, and n is an integer in the range from oneto three inclusive: (b) self-condensation polymers of those compounds ofFormula I in which R and X are hydrogen atoms, n is one, and Y is ahydrocarbon radical; and (c) compounds having the structural Formula III'IOGUP CIlaOH where R is an alkyl group having less than four carbonatoms and Y is the same as in structural Formula I, the proportion ofdihydric phenol to phenolic dialkanol being from 20:80 to :20 by weight;and (3) a liquid medium for the solid phenolic components, said solidcomponents being from 5 to 15% of the total weight; (B) volatilizing theliquid medium from the coated nylon textile material; (C) placing theresulting adhesive-coated nylon textile material in direct and intimatecontact with the unvulcanized rubber compounded with a resin-type curingagent selected from the group consisting of 2,6-dirnethylol-4-hydrocarbonphenols and the self-condensation polymers thereof; and (D)curing the resulting rubber-nylon composite.

2. A method of bonding nylon textile material to rubher as in claim 1,wherein a self-condensation polymer of2,6-dimcthylol-4-hydrocarbonphenol is used as curing agent for therubber.

3. A method of bonding nylon textile material to rubber, said rubberbeing a copoiymer of an isoolefin with a minor amount of a multiolefinic'unsaturate, comprising (A) passing said nylon textile material at arate of from 2 to 16 yards per minute into and through a bath ofadhesive composition comprising: (1) a compound selected from the groupconsisting of dihydric phenols of the benzene and naphthalene seriesintimately mixed with (2) a phenolic dialkanol compound having thestructural formula -C lIx- ClIzOX where R and X independently areselected from the group consisting of hydrogen atoms and acyl radicalshaving less that 4 carbon atoms, and where Y is selected from the groupconsisting of chlorine atoms, and alkyl, cycloalkyl, aryl, aralkyl, andnitro radicals, and n is an integer in the range from one to threeinclusive, the proportion of said dihydric phenol to phenolic dialkanolbeing from 20:80 to 80:20 by weight and 3) a liquid medium for the solidphenolic components, said solid components being from to of the totalweight; (B) volatilizing the liquid medium from the coated nylon textilematerial; (C) placing the resulting adhesive coated nylon textilematerial in direct and intimate contact with the unvulcanized rubbercompounded with a resin-type curing agent selected from the groupconsisting of 2,o-dimethylol-4-hydrocarbonphenols and theself-condensation of polymers thereof; and (D) curing the resultingrubber-nylon composite.

4. A method of bonding nylon textile material to null)- ber, said rubberbeing a copolymer of an isoolefin with a minor amount of a multiolefinicunsaturate, comprising (A) passing said nylon textile material at a rateof from 2 to 16 yards per minute into and through a bath of adhesivecomposition comprising: (1) a compound selected from the groupconsisting of dihydric phenols of the benzene and naphthalene seriesintimately mixed with (2) a phenolic dialkanol compound which is aself-condensation polymer of compounds having the structural formulaI'IOCH; CIlzOH where Y is a hydrocarbon radical, the proportion of saiddihydric phenol to said phenollc dialkanol being from :80 to 80:20 byweight, and (3) a liquid medium for the solid phenolic components, saidsolid components being from 5 to 15% of the total weight; (B)volatilizing the liquid from the coated nylon textile material; (C)placing the resulting adhesive coated nylon textile material in directand intimate contact with the unvu lcanized rubber which has beencompounded with a resin-type curing agent selected from the groupconsisting of 2,6-dimethylol-4- hydrocarbonphcnol and theself-condensation polymers thereof; and (D) curing the resultingrubber-nylon composite.

5. A method of bonding nylon textile material to rubher, said rubberbeing a copolymer of an isoolefin with a minor amount of a multiolelinicunsaturate, comprising (A) passing said nylon material at a rate of from2 to 16 yards per minute into and through a bath of adhesive compositioncomprising: (1) a compound selected from the group consisting ofdihydric phenols of the benzene and naphthalene series intimately mixedwith (2) a phenolic dialkanol compound having the structural formulawhere R is an alkyl group having less than four carbon atoms and Y isselected from the group consisting of chlorine atoms, and alkyl,cycloalkyl, aryl, aralkyl, and nitro radicals, the proportion of saiddihydric phenol to said phenolic dialkanol being from 20:80 to 80:20 byWeight, and (3) a solvent for the solid phenolic components, said solidcomponents being from 5 to 15% of the total weight; (B) volatiiizing thesolvent from, the coated nylon textile material; (C) placing theresulting adhesive coated nylon textile material in direct and intimatecontact with the uuvulcanized rubber which has been compounded with aresin-type curing agent selected from the group consisting of2,6-dimethylol-4-hydrocarbonphenol and the self-condensation polymersthereof; and (D) curing, the resulting rubber-nylon composite.

6. An adhesive composition for bonding rubber, said rubber being acopolymer of an isoolefin with a minor amount 01 a multiolefinicunsaturate, to nylon textile material comprising: (1) a compoundselected from the group consisting of dihydric phenols of the benzeneand naphthalene series intimately mixed with (2) a phenolic dialkanolmaterial selected from the group consisting of (a) compounds having thestructural Formula I XL u (I) where R and X independently are selectedfrom the group consisting of hydrogen atoms and acyl radicals havingless than 4 carbon atoms, and where Y is selected from the groupconsisting of chlorine atoms, and alkyl, cycloalkyl, aryl, aralkyl, andnitro radicals, and n is an integer in the range from one to threeinclusive; (b) self-condensation polymers of those compounds of FormulaI in which R and X are hydrogen atoms, n is one, and Y is a hydrocarbonradical; and (c) compounds having a structural Formula II Where R is analkyl group having less than four carbon atoms and Y is the same as instructural Formula I, the proportion of said dihydric phenol to saidphenolic dialkanol being from 20:80 to :20 by weight; and (3) a liquidmedium for the solid phenolic components, said solid components beingfrom 5 to 15% of the total weight.

7. An adhesive composition for bonding rubber, said rubber being acopolymer of an isoolefin with a minor amount of a multiolefinicunsaturate, to nylon textile material comprising a compound selectedfrom the group consisting of dihydric phenols of the benzene andnaphthalene series intimately mixed with a phenolic dialkanol compoundhaving the structural formula X0 -cIIi J cmox i Y n where R and Xindependently are selected from the group consisting of hydrogen atomsand acyl radicals having less than 4 carbon atoms, and where Y isselected from the group consisting of chlorine atoms, and alltyl,cycloaiky'l, aryl, aralkyl, and nitro radicals; and n is an integer inthe range from one to three inclusive, the proportion of said d ihydricphenol to said phenolic dialkanol being from 20:80 to 80:20 by weightand a liquid medium for the solid phenolic components, said solidcomponents being from 5 to 15% of the total weight.

8. An adhesive composition for bonding rubber to nylon textile materialas in claim 7, wherein the phenolic dialkanol is2,6-dimethylol-4-tert-butylphenol.

9. An adhesive composition for bonding rubber to 11 nylon textilematerial as in claim 8, wherein the dihydric phenol is hydroquinone.

10. An adhesive composition for bonding rubber to nylon textile materialas in claim 8, wherein the dihydric phenol is resorcinol.

11. An adhesive composition for bonding rubber, said rubber being acopolymer of an isoolefin with a minor amount of a multiolefinicunsaturate, to nylon textile material comprising a compound selectedfrom the group consisting of dihydric phenols of the benzene andnaphthalene series intimately mixed with a phenolic dialkanol compoundwhich is a self-condensation polymer of compounds having the structuralformula OIII IIOCIIT CHzOII where Y is a hydrocarbon radical, theproportion of said dihydric phenol to said phenolic dialkanol being from20:80 to 80:20 by weight, and a liquid medium for the solid phenoliccomponents, said solid components being from 5 to of the total weight.

12. An adhesive composition for bonding rubber, said rubber being acopolymer of an isoolefin with a minor amount of a multiolefinicunsaturate, to nylon textile material comprising a compound selectedfrom the group consisting of dihydric phenols of the benzene andnaphthalene series intimately mixed with a phenolic dialkanol compoundhaving the structural formula IIOCHw- CHzOH where R is an alkyl grouphaving less than four carbon atoms and Y is selected from the groupconsisting of chlorine atoms, and alkyl, eycloalkyl, aryl, aralkyl, andnitro radicals, the proportion of dihydric phenol to phenolic dialkanolbeing from 80:20 to :80 by weight, and a solvent for the solid phenoliccomponents, said solid components being from 5 to 15% of the totalWeight.

13. A vulcanizate of alternate layers of rubber, said rubber being acopolymer of an isoolefin with a minor amount of multiolefinicunsaturate admixed with a resintype curing agent selected from the groupconsisting of 2,6-dimethylol-4-hydrocarbonphenol and theself-condensation polymers thereof, and nylon textile material coatedwith from 0.75 to 5.0% by weight of an adhesive comprising (1) acompound selected from the group consist- 12 ing of dihydric phenols ofthe benzene and naphthalene series and (2) a phenolic dialkanol compoundselected from the group consisting of (a) compounds having thestructural Formulal X0 -CII1- CllzOX i Y I1 where R and X independentlyare selected from the group consisting of hydrogen atoms and acylradicals having less than 4 carbon atoms, and where Y is selected fromthe group consisting of chlorine atoms, and alkyl, cycloalkyl, aryl,aralkyl, and nitro radicals, and n is an integer in the range from oneto three inclusive, (b) self-condensation polymers of those compounds ofFormula I in which R and X are hydrogen atoms, n is one, and Y is ahydrocarbon radical, and (c) compounds having the structural Formula IIIIOCIIP C H2011 where R is an alkyl group having less than four carbonatoms and Y is the same as in structural Formula I, the the proportionof dihydric phenol to phenolic dialkanol being from 20:80 to :20 byweight.

14. A vulcanizate as in claim 13, wherein a self-condensation polymer of2,6-dirnethanol-4-hydrocarbonphenol is employed as the resin-type curingagent for the rubber.

15. A vulcanizate as in claim 14, wherein the dihydric phenol (1) ishydroquinone and the phenolic dialkanol compound (2) is2,6-dimethylol-4-tert-butylphenol.

16. A vulcanizate as in claim 14, wherein the dihydric phenol (l) isresorcinol and the phenolic dialkanol compound (2) is2,6-dimethylol-4-tert-butylphenol.

References Cited in the tile of this patent UNITED STATES PATENTS2,346,290 Loughborough May 23, 1944 2,414,414 Rhodes Jan. 14, 19472,701,895 Tawney et al Feb. 15, 1955 2,739,918 lll'ingworth Mar. 27,1956 2,830,970 Tawney Apr. 15, 1958 2,839,443 Fleming June 22, 1958

13. A VULCANIZATE OF ALTERNATE LAYERS OF RUBBER, SAID RUBBER BEING ACOPOLYMER OF AN ISOLEFIN WITH A MINOR AMOUNT OF MULTIOLEFINIC UNSATURATEADMIXED WITH A RESINTYPE CURING AGENT SELECTED FROM THE GROUP CONSISTINGOF 2,6-DIMETHYOL-4-HYDROCARBONPHENOL AND THE SELF-CONDENSATION POLYMERSTHEEOF, AND NYLON TEXTILE MATERIAL COATED WITH FROM 0.75 TO 5.0% BYWEIGHT OF AN ADHESIVE COMPRISING (1) A COMPOUND SELECTED FROM THE GROUPCONSISTING OF DIHYDRIC PHENOLS OF THE BENZENE AND NAPHTHALENE SERIES AND(2) A PHENOLIC DIALKANOL COMPOUND SELECTED FROM THE GROUP CONSISTING OF(A) COMPOUNDS HAVING THE STRUCTURAL FORMULA I